Synthesis of novel acrylic modified water reducible alkyd resin: Investigation of acrylic copolymer ratio effect on film properties and thermal behaviors

New four‐component water reducible acrylic modified alkyd resins that are based on 1,3‐propanediol and contain different ratios of acrylic copolymer (AC) were synthesized by using a novel four‐stage fatty acid method. The final content of solids in the water reducible acrylic modified alkyd resins was 60% by weight. After the modified alkyd resin films were cured at 150°C for 1 h, it was observed that the use of AC as the modifier component had improved their physical and chemical surface coating properties and thermal behaviors. Experimental results show that the optimum AC ratio is 40% of the equivalent amount of AC to alkyd resin. Low‐volatile organic compounds (VOC) content water reducible acrylic modified alkyd resins yielded soft and flexible films with high chemical/thermal resistance, suitable for manufacturing of surface coating binders. POLYM. ENG. SCI., 56:947–954, 2016. © 2016 Society of Plastics Engineers     

Effect of different polymers on the efficiency of water‐borne methyl amine adduct as corrosion inhibitor for surface coatings

Styrene/acrylic emulsion copolymer and water‐based short oil urethane alkyd resin were used as binders to prepare water‐based, environmentally friendly paints by using 0.5% emulsified methylamine adduct as corrosion inhibitor. The choice of the two above‐mentioned binders was based on the fact that styrene/acrylic emulsion copolymer is a nonconvertible binder, whereas short oil urethane alkyd resin is a convertible binder. The physical, chemical, mechanical, and corrosion properties of the paint films were evaluated and compared with a commercially known anticorrosive water‐based paint. It was found that the prepared paints have unique desirable properties such as the following: they do not contain anticorrosive pigments (which contain heavy metals in their main chemical structure); they are solvent‐free; and they can be produced to match any color. Corrosion tests on the films of the formulated paints revealed that the short oil urethane alkyd resin is superior to the styrene/acrylic copolymer. Moreover, the corrosion inhibition properties of the paint films prepared from both binders are comparable with the commercially available paints containing anticorrosive pigments. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 879–885, 2002     

The effect of alkyd resins on the properties of AA‐NC semi‐IPNs as binders in wood finish

Wood coatings of AA‐NC semi‐interpenetrating polymer networks (semi‐IPNs), made from acid curing amino‐alkyd resins (AA) and nitrocellulose (NC), were prepared by sequential polymerization method. To investigate the effects of oil length on the properties of AA‐NC semi‐IPNs, three grades of alkyd resins (Alkyd) containing 38, 48, and 58% oil were synthesized with phthalic anhydride, glycerol, and soybean oil, employing alcoholysis method. The butylated urea formaldehyde resin (UF) and melamine formaldehyde resin (MF) were also prepared in this study. The AA‐NC semi‐IPNs were maintained at a weight ratio of AA : NC of 25 : 75, where the AA was the composition of MF : UF : Alkyd of 7.5 : 22.5 : 70 (by weight), and 10% of p‐toluene sulfonic acid solution (concentration, 25% in isopropyl alcohol) based on the weight of amino resins was added as acid catalyst. The properties of coatings such as viscosity, drying time, and gel time, and the properties of films including adhesion, hardness, abrasion resistance, impact resistance, tensile strength, released formaldehyde, lightfastness, solvent resistance, and durability were examined. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1923–1927, 2004     

Factors influencing the stability and film properties of acrylic/alkyd water-reducible hybrid systems using a response surface technique

Acrylic-grafted-alkyd resins were prepared by free radical chemistry. Long, medium, and short oil alkyds were prepared using soybean oil, glycerol, phthalic anhydride (PA), and tetrahydrophthalic anhydride (THPA) and used as the alkyd phase. Acrylic co-monomer formulas containing methyl methacrylate (MMA), butyl acrylate (BA), methacrylic acid (MAA), and vinyl trimethoxysilane (VTMS) were polymerized in the presence of the different alkyds using 2,2′-azobisisobutyronitrile (AIBN) as the initiator to obtain the final grafted structures. Design of experiments was used to understand how different variables in the synthesis of the acrylated-alkyds affect the film performance. A Box–Behnkin design was used, varying the oil length of the alkyd phase, the degree of unsaturation in the polyester backbone, and acrylic to alkyd ratio. Acrylic–alkyd hybrid resins were reduced with an amine/water mixture. The hydrolytic stability of hybrid alkyd dispersed in water was evaluated. Cured films were prepared and basic coatings properties were also evaluated. It was found that the oil length of the alkyd is the most dominant factor for final coatings properties of the resins. The hydrolytic stability was dependent on the acrylic to alkyd ratio. The oil length of the alkyd backbone had a minimal effect on stability of the resin and film performance.     

Improving coating characteristics of palm stearin alkyd by modification with ketone resin

The present study describes the modification of long oil palm stearin based alkyd resin through blending it with a commercially available ketone resin to improve its coating characteristics. The effects of blending on air drying time, hardness, adhesion, gloss, impact strength, chemical resistance and thermal behavior of dried films of blends were investigated and compared to virgin alkyds. It was found that blending results in modifying coating characteristics of palm stearin based alkyd resins, significantly. Best result was observed for weight ratio 70:30 of alkyd and ketone resins.     

The use of aminolysis,aminoglycolysis, and simultaneous aminolysis–hydrolysis products of waste PET for production of paint binder

This work is concerned with the use of aminolysis, aminoglycolysis, and simultaneous aminolysis–hydrolysis products of waste PET for production of paint binder based on alkyd resin. For this purpose, first, aminolysis, aminoglycolysis, and simultaneous hydrolysis–aminolysis reactions of waste PET were carried out in the presence of different chemical agents in xylene medium at high pressures. Reactions of waste PET flakes obtained from grinding postconsumer water bottles were carried out in an autoclave at higher temperatures. Then, four alkyd resins, formulated to have oil content 40–50%, were prepared using these depolymerization products. One of resins is “reference alkyd resin” which was prepared by using soybean oil fatty acid, phthalic anhydride, glycerine, and ethylene glycol for comparison. Other three alkyds are “depolymerization product‐based alkyd resins” in which depolymerization products is used instead of ethylene glycol. Then, the physical and chemical surface coating properties and thermal behaviors of alkyd resins films were investigated comparatively. As a result, we concluded that aminolysis, aminoglycolysis, and simultaneous aminolysis‐hydrolysis products of waste PET are suitable for manufacturing both air drying and oven curing paint binder based on alkyd resins. The film prepared from alkyd resin based on simultaneous aminolysis‐hydrolysis product showed extremely good surface coating properties and thermal stability. POLYM. ENG. SCI., 54:2272–2281, 2014. © 2013 Society of Plastics Engineers     

Novel synthesis of carboxy-functional soybean acrylic-alkyd resins for water-reducible coatings

A new process was developed for synthesis of alkyd resins in which a conventional monoglyceride is reacted with a carboxy-functional acrylic copolymer. The novel products are called acrylicalkyd resins. The carboxy-functional acrylic copolymers were synthesized by solution-free radical polymerization. Gelation during alkyd resin synthesis was avoided by: (1) limiting the molecular weight of the acrylic copolymers to M_n 3500–5000 and (2) limiting the number average functionality about 6.5–10 carboxyl groups per molecule. Further, the carboxyl groups were derived from a mixture of acrylic and methacrylic acids (1/1.2 mol ratio) in the expectation that this would help control the process. Three series of acrylic copolymers were prepared from various combinations of acrylic monomers and reacted with a monoglyceride prepared from soybean oil and trimethylol propane. The composition of the acrylic resin was adjusted to minimize phase separation [observed visually and by scanning probe microscopy (SPM)] within cast films. The most satisfactory results were obtained with copolymers of 62–71 wt% of methyl methacrylate, 5–21 wt% of lauryl methacrylate, 7.2 wt% of acrylic acid, and 10.3 wt% of methacrylic acid. In preliminary tests, waterborne coatings made from acrylic-alkyd resins based on these acrylics had excellent stability, with acid numbers changing less than 10% after nine months of storage. Coatings Research Institute Ypsilanti MI 48197 Department of Physics, Ypsilanti, MI 48197.     

Effects of urea formaldehyde resin to film properties of alkyd–melamine formaldehyde resins containing organo clay

Organo clay modified alkyd resins were prepared and these modified alkyd resins were cured with different ratios of melamine formaldehyde and urea formaldehyde resins in this work. Alkyds formulated to have oil content 40% were prepared with phthalic anhydride (PA), glycerine (G), coconut oil fatty acid (COFA), dipropylene glycol (DPG) and organo clay. “K alkyd constant system” was used for the formulation calculations of the alkyd resins. Alkyd resins were blended with 40% of a commercial melamine formaldehyde. The films of the alkyd–amino resins were prepared from 60% solid content xylene solutions using 50 μm applicators. After the films were cured at 140 °C for 2 h in an oven, properties of the films were determined. The film properties of the alkyd–amino resins such as drying degree, hardness, adhesion strength, abrasion resistance, water, acid, alkaline, solvent resistance, and resistance to environmental conditions were investigated. The addition of the urea formaldehyde resin and organo clay has positive effect on the physical and chemical resistance of the alkyd–amino resins.     

Investigation of the effect of hydrolysis products of postconsumer polyethylene terephthalate bottles on the properties of alkyd resins

Hydrolysis of waste polyethylene terephthalate (PET) flakes obtained from grinding postconsumer bottles was carried out at 200–230°C and molar ratios of PET/H₂O were taken as 1/5; 1/10; 1/20. The reaction products, when extracted with boiling water, yielded a water soluble crystallizable fraction (WSCF) and a water insoluble fraction (WIF). These fractions were characterized by acid and hydroxyl value determinations and DSC analysis. WSCF and WIF were used for preparation of alkyd resins. Five long oil alkyd resins were prepared from phthalic anhydride (PA) (reference alkyd resin) or hydrolysis products of the waste PET (PET‐based alkyd resin), pentaerithrithol (PE), soybean oil fatty acid (SOFA), and ethylene glycol (EG). Film properties and thermal degradation stabilities of these alkyd resins were investigated. Drying time, hardness, alkaline resistance, and thermal oxidative degradation resistance of the PET‐based alkyd resins are better than these properties of reference resin. The results show that hydrolysis products of waste PET obtained from postconsumer bottles are suitable for manufacturing of alkyd resins. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Rubber seed oil modified with maleic anhydride and fumaric acid and their alkyd resins as binders in water‐reducible coatings

Rubber seed oil (RSO) was modified with different amounts of maleic anhydride, and RSO alkyds (50% oil length) were modified to various extents by the incorporation of different amounts of maleic anhydride and fumaric acid. All the resins were evaluated as water‐reducible binders. Modification with maleic anhydride increased the acid and saponification values of RSO but reduced the iodine value. RSO modified with maleic anhydride exhibited lower amounts of volatile organic compounds (<20 g/L) than the corresponding RSO alkyds (34–87 g/L). The alkyd samples were superior to the modified RSO in chemical resistance. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3256–3259, 2003     

Preparation and characterization of water reducible alkyd resin/colloidal silica nanocomposite coatings

In this study, water reducible alkyd resins containing different amounts of colloidal silica were synthesized for the first time. In order to achieve this, alkyd resin, which has an oil content of 35%, was prepared with tall oil fatty acid, isophthalic acid, trimellitic anhydride, and trimethylolpropane. The alkyd resin was neutralized with triethylamine, and was dissolved in an isobutyl alcohol-isopropyl alcohol-butyl glycol mixture to produce 75% (wt.) solution, which was called stock alkyd resin. The stock alkyd resin was diluted with water to 50% (wt.) concentration with water and colloidal silica mixture in order to prepare an alkyd solution containing 0%, 5%, 10%, 15% and 20% colloidal silica. Then the effect of the silica nanoparticle addition on the surface coating properties, thermal behaviors and surface morphologies of water reducible alkyd resins was investigated. As a result, the addition of colloidal silica has improved surface coating properties and thermal behaviors of nanocomposite water reducible alkyd resin.     

Synthesis of four-component acrylic-modified water-reducible alkyd resin: investigation of dilution ratio effect on film properties and thermal behaviors

This study investigated the effect of the dilution ratio on film properties of acrylic-modified water-reducible alkyd resins. First, new four-component acrylic-modified alkyd resins based on 1,3-propanediol containing 40% of the equivalent amount of acrylic copolymer to alkyd resin were synthesized using the fatty acid method. The synthesized acrylic-modified alkyd resin was then dissolved in isopropyl alcohol (IPA) at various ratios and further diluted using distilled water at various ratios to obtain by-weight percentages of 70/50, 70/60, and 80/60 of solid content to IPA and water, respectively. Films of the modified alkyd resins were prepared, and cured at 150°C for 1 h, then their physical and chemical surface coating properties and thermal behaviors were investigated. The best results were obtained for the by-weight percentages of 80/60.     

Preparation of epoxy resin/acrylic composite latexes by miniemulsion polymerization method

Epoxy resin/acrylic composite latexes were prepared by miniemulsion polymerization. Epoxy resins have a functional epoxy group in them and excellent characteristics, such as heat resistance and good adhesion. Acrylic latexes have weather and water resistance. Combining the epoxy resin and the acrylic latex was an attempt to actualize these advantages. The miniemulsion polymerization method was effective in obtaining the composite latex. A less than 500‐nm droplet size for the monomer preemulsion was necessary to obtain the latex in a stable manner. Dimethylaminoethylmethacrylate and methacrylic acid as the reactive functional monomer with an epoxy group were introduced to the latexes. The effect of the polymerization method of these functional groups on the properties of latexes and their films was investigated. The latex prepared by the two‐stage polymerization method had good polymerization stability, storage stability, and solvent resistance. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 128–133, 2001     

LLDPE‐based mono‐ and multilayer blown films: Property enhancement through coextrusion

In this study we investigated the performance of multilayer coextruded linear low‐density polyethylene (LLDPE) blown films. Five‐layer films were compared with monolayer dry‐blended films, and the effects of layer composition and layout on the end‐use properties of the coextruded films were highlighted. Three different LLDPEs were used: a conventional Ziegler‐Natta LLDPE gas phase butene copolymer, an advanced Ziegler‐Natta LLDPE solution octene copolymer, and a single‐site LLDPE solution octene copolymer. Numerous five‐layer coextruded structures comprising the single‐site resin and the other two Ziegler‐Natta resins were produced. The coextruded structures composed of the LLDPE butene and the single‐site resin yielded improved end‐use properties relative to the monolayer‐blended films. This result was ascribed to the presence of interfacial transcrystalline layers. Also, blends of the single‐site LLDPE and the advanced Ziegler‐Natta LLDPE octene resins within selected layers of coextruded films showed slightly enhanced tear resistance. Finally, it was found that haze was significantly reduced when the outside layers were composed of the single‐site resin. POLYM. ENG. SCI., 45:1222–1230, 2005. © 2005 Society of Plastics Engineers     

Effect of molecular structure on performance of electroactive ionic acrylic copolymer–platinum composites

The character and performance of a new ionic polymer–metal composite (IPMC) prepared with a melt‐processable fluorinated acrylic copolymer were examined. The fluorinated acrylic copolymer was synthesized by the copolymerization of fluoroalkyl methacrylate (DuPont Zonyl) and acrylic acid, and it was compression molded to attain membranes of various thicknesses. The current and displacement responses by electric stimulus were measured to study the effects of the ionic concentration, thickness, and countercation on the actuation of the IPMC. The ionic center of the acrylic copolymer was essential for the actuation of the IPMC; however, too much ionic center induced excessive water uptake, which caused adverse effects on the performance of the IPMC. When the applied voltage was 5 V, the largest current and displacement responses were observed with the IPMC prepared by a fluorinated acrylic copolymer containing 11.8 wt % acrylic acid. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1732–1739, 2005     

A novel type of Si‐containing acrylic resins: Synthesis,characterization, and film properties

A novel type of Si‐containing acrylic resins was prepared by two steps and investigated their usage as surface coatings materials. At first a reactive polysiloxane intermediate Z‐6018 was reacted with 2‐hydroxyethyl methacrylate (HEMA) in toluene at 110°C under N₂ atmosphere. After the condensation reaction was stopped, reacted with different acrylic ester monomers such as ethyl acrylate (EA) and methyl methacrylate (MMA) at different mole ratio (1/3 and 1/4) by the free radical addition polymerization. Structures of Si‐containing acrylic resins were characterized by Fourier Transform Infrared Spectrometer (FTIR) and thermal properties of these resins were investigated by thermogravimetric analysis and differential scanning calorimetry DSC techniques. Surface coating properties of the films prepared from these resin were also determined. The results showed that all films are flexible, glossy or semi gloss and have excellent drying and adhesion properties. All films also exhibit abrasion resistances moderately. Water resistance of the films was generally modified by cured in oven and alkaline resistance of the films prepared from resins containing ethyl acrylate units are excellent. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Stability and film properties of tung oil modified soybean alkyd emulsion

A series of tung oil modified soybean alkyd emulsions are prepared by an inversion emulsified technique. In these alkyd resins, the tung oil contents are about 0, 12.5, and 25.0 wt % (based on the total oil). Using IGEPAL CO‐630 as the surfactant, a very stable alkyd emulsion can be obtained. With the increase of the tung oil contents in alkyd emulsions, the initial droplet sizes of the emulsions increase dramatically. Aging under 50°C can eliminate the difference in droplet sizes; the final droplet sizes of the emulsions are about 50 nm. The alkyd resins also have good hydrolytic stability. The tung oil contents in the alkyd resins also strongly influences the film properties; suitable tung oil content improves the film gloss. An atomic force microscopy investigation shows that the film from the alkyd emulsion is more water sensitive; after a 50‐h deionized water immersion, the film surface appears to have a lot of dents. This indicates that the film surface may be very rich in surfactant species. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1698–1706, 2000     

Structure of tall oil fatty acid-based alkyd resins and alkyd–acrylic copolymers studied by NMR spectroscopy

One- and two-dimensional NMR spectroscopy was used to evaluate the structure of tall oil fatty acid (TOFA)-based alkyd resins and waterborne alkyd–acrylic copolymers. An increase in the functionality of the polyol that is used in the alkyd resin synthesis was found to increase the reactivity of the polyol towards the diacid compared with the TOFA, which causes the formation of more branched and higher molar mass alkyd resin structures. During the copolymerization, polyacrylate chains were grafted to the double bonds and allylic sites of the fatty acid chains in the alkyd resin. Butyl acrylate preferentially grafted to the double bonds, while methyl methacrylate tended to graft to the allylic position. High proportions of the double bonds remaining after copolymerization were crucial to the film formation of copolymers, because the chemical drying of copolymer films occurred by an autoxidation process.     

Styrene–hydroxyethyl acrylate copolymer based alkyd resins with a comb‐type structural morphology obtained with a high solid content

Nowadays, so many studies are being carried out with the goal of obtaining environmentally friendly materials. In this study, styrene–hydroxyethyl acrylate copolymer (St‐co‐HEA) based alkyd resins with high solid contents and comb‐type structural morphologies were synthesized from St‐co‐HEA and macromonomers [MMs; dimethylol propionic acid modified with different proportions of tall oil fatty acids (TOFAs)]. The molar mass and gloss values of St‐co‐HEA were lower than those of the alkyd resins, but the thermal stability, viscosity, and glass‐transition temperature exhibited the opposite behavior. In all cases, the conversion percentage was higher than 80 %. The hydroxyl value and viscosity of the alkyd resins decreased with the TOFA content present in the MMrs, but the molar mass and the thermal stability increased. The rheological behavior of these resins was mainly pseudoplastic. Furthermore, the viscosity values were lower than 10 Pa s. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43996.     

Design and synthesis of bio-based epoxidized alkyd resin for anti-corrosive coating application

Alkyd resins with long aliphatic chain in their backbone are not suitable for high-performance applications. To overcome this limitation of alkyd resins, their backbone structure is usually chemically modified. In this study, an alkyd resin was successfully synthesized from renewable resources, including itaconic acid and linseed oil. Subsequently, the unsaturated backbone of the alkyd resin was converted to oxirane ring through epoxidation reaction in the presence of hydrogen peroxide and acetic acid. The epoxidized alkyd (EA) resin backbone was modified with various amounts of 3-amino propyltrimethoxysilane (APTMS) from 10 to 40 mol percent to enhance the anti-corrosive properties of coatings prepared from the alkyd resins. The structural elucidation of synthesized resins was described by physicochemical analysis and Fourier transform infrared and ¹H nuclear magnetic resonance spectroscopies. The EA resin and APTMS-modified EA resin were cured by itaconic acid in 1:1 stoichiometric ratio on the equivalent weight basis. The differential scanning calorimetric and thermogravimetric analysis results showed that thermal properties improved with increasing APTMS content. The cured coatings were characterized for their mechanical properties, chemical and solvent resistance, gel content, and water absorption. The corrosion-resistance performance of coatings was evaluated by electrochemical impedance spectroscopy and salt-spray test. It was observed that the highly cross-linked structure of the APTMS-modified EA coatings enhanced the corrosion protective property of coating films.